Compounds comprising triazine group, fluorene-group and hetero-fluorene group

ABSTRACT

The present invention relates to a compound according to formula 1: 
                         
suitable for use as a layer material for electronic devices, and to an organic semiconductor layer comprising at least one compound according to formula 1, as well as to an organic electronic device comprising at least one organic semiconductor layer, and a method of manufacturing the same.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to European Patent Application No. 17200894.8, filed Nov. 9, 2017, which is incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to compounds, in particular to compounds with a triazine group, fluorene group and hetero-fluorene group, suitable for use as a layer material for electronic devices, and to an organic semiconductor layer comprising at least one compound thereof, as well as to an organic electronic device comprising at least one organic semiconductor layer, and a method of manufacturing the same.

BACKGROUND ART

Organic electronic devices, such as organic light-emitting diodes OLEDs, which are self-emitting devices, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.

When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML, via the HTL, and electrons injected from the cathode move to the EML, via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced, so that an OLED having the above-described structure has excellent efficiency and/or a long lifetime.

Performance of an organic light emitting diode may be affected by characteristics of the organic semiconductor layer, and among them, may be affected by characteristics of an organic material of the organic semiconductor layer.

Particularly, development for an organic material being capable of increasing electron mobility and simultaneously increasing electrochemical stability is needed so that the organic electronic device, such as an organic light emitting diode, may be applied to a large-size flat panel display.

WO2017171376 relates to a compound of the chemical formula 1 and an organic electronic element comprising the compound.

There remains a need to improve performance of organic semiconductor layers, organic semiconductor materials, as well as organic electronic devices thereof, in particular to achieve increased lifetime and higher efficiency through improving the characteristics of the compounds comprised therein.

There is a need for alternative organic semiconductor materials and organic semiconductor layers as well as organic electronic devices having increased lifetime and/or improved efficiency at low operating voltage.

In particular there is a need for alternative compounds having increased lifetime as well as improved efficiency and at the same time keeping the operating voltage and thereby the power consumption low to deliver long battery life for example mobile electronic devices.

DISCLOSURE

An aspect of the present invention provides a compound of formula 1,

-   wherein     -   X is selected from O or S;     -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or         unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃         to C₃₆ heteroaryl;     -   Ar² is selected from C₁ to C₁₆ alkylene or is selected from         unsubstituted arylene (C7) to (C11):

-   -   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or         unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃         to C₃₆ heteroaryl; and     -   wherein         -   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃             to C₃₆ heteroaryl is mono or di-substituted, wherein             -   the substituents of the substituted C₆ to C₂₄ aryl and                 substituted C₃ to C₃₆ heteroaryl are selected from C₁ to                 C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated                 C₁ to C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆                 alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN;                 and     -   wherein         -   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃             to C₃₆ heteroaryl is mono or di-substituted, wherein

-   the substituents of the substituted C₆ to C₃₆ aryl and substituted     C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆ alkyl, C₁ to C₁₆     alkoxy, partially or perfluorinated C₁ to C₁₆ alkyl, partially or     perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅     heteroaryl, F or CN

According to another embodiment a compound of formula 1, is provided

-   wherein -   X is selected from O or S; -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; -   Ar² is selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene; -   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;     and -   wherein     -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆         heteroaryl of Ar¹ is mono or di-substituted; and -   wherein     -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆         heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S, preferably O; -   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆         alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈         aryl, C₃ to C₂₅ heteroaryl, F or CN, preferably preferably from         C₁ to C₁₆ alkyl; -   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, wherein     -   the substituents of the substituted C₆ to C₃₆ arylene are         selected from C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially or         perfluorinated C₁ to C₁₆ alkyl, partially or perfluorinated C₁         to C₁₆ alkoxy, F or CN, preferably from C₁ to C₁₆ alkyl; -   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₃₆ arylene and         substituted C₃ to C₃₆ heteroarylene are selected from C₁ to C₁₆         alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆         alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈         aryl, C₃ to C₂₅ heteroaryl, F or CN, preferably from C₁ to C₁₆         alkyl;     -   wherein substituted Ar¹ and/or Ar³ is mono or di-substituted.

The Ar¹ group is connected via a single bond to the triazine group of the compound of formula 1. Mono or di-substituted Ar¹ means throughout the specification that for mono-substituted Ar¹ the Ar¹ group comprises one additional substituent and for di-substituted Ar¹ the Ar¹ group comprises two additional substituents, which can be independently selected.

The Ar³ group is connected via a single bond to a fluorene group of the compound of formula 1. Mono or di-substituted Ar³ means throughout the specification that for mono-substituted Ar³ the Ar³ group comprises one additional substituent and for di-substituted Ar³ the Ar³ group comprises two additional substituents, which can be independently selected.

Hetero atoms if not otherwise stated can be individually selected from N, O, S, B, Si, P, Se, preferably from N, O and S and more preferred is N.

According to one embodiment the compound is represented by formula 1, wherein Ar² selected from carbazolylene is excluded.

According to one embodiment the compound of formula 1,

-   can be further defined, wherein -   X can be selected from O or S; -   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN; -   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, wherein     -   the substituents of the substituted C₆ to C₃₆ arylene are         selected from C₁ to C₁₆ alkyl or CN; -   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN; and -   wherein     -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆         heteroaryl of Ar¹ is mono or di-substituted; and -   wherein     -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆         heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1,

-   wherein -   X is selected from O or S, preferably O; -   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ to C₁₆     alkyl, substituted C₆ to C₂₄ aryl, preferably unsubstituted C₆ to     C₁₈ aryl or C₁ to C₁₆ alkyl, substituted C₆ to C₁₈, and further     preferred unsubstituted C₁₂ to C₁₈ aryl or C₁ to C₆ alkyl     substituted C₁₂ to C₁₈, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN; -   Ar² is selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, preferably phenylene or biphenylene     and more preferred phenylene, wherein     -   the substituents of the substituted C₆ to C₃₆ arylene are         selected from C₁ to C₁₆ alkyl or CN; -   Ar³ is selected from unsubstituted C₆ to C₂₄ aryl, preferably phenyl     or biphenyl and in addition preferred phenyl, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S; -   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₂₄ aryl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl are selected         from C₁ to C₁₆ alkyl or C₆ to C₁₈ aryl; -   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, wherein     -   the substituents of the substituted C₆ to C₃₆ arylene are         selected from C₁ to C₁₆ alkyl; -   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₃₆ aryl, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl are selected         from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl; -   wherein substituted Ar¹ and/or Ar³ is mono or di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl; -   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, wherein the substituents of the     substituted C₆ to C₃₆ arylene are selected from C₁ to C₁₆ alkyl; -   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl; -   wherein substituted Ar¹ and/or substituted Ar³ is mono or     di-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl; -   Ar² can be selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene, wherein the substituents of the     substituted C₆ to C₃₆ arylene are selected from C₁ to C₁₆ alkyl; -   Ar³ can be selected from C₁ to C₁₆ alkyl, substituted or     unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to     C₃₆ heteroaryl, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl; -   wherein substituted Ar¹ and/or substituted Ar³ is mono-substituted.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl or     unsubstituted C₆ to C₂₄ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl or     unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O or S; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl or     unsubstituted C₆ to C₂₄ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl or     unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl or     unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl or     unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₁₂ aryl or     unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ aryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl; -   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene; -   Ar³ can be selected from unsubstituted C₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ aryl; -   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene; -   Ar³ can be selected from unsubstituted C₆ aryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₂₄ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₃₆ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₂₄ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₂₄ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from O; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment of the compound of formula 1, wherein

-   X can be selected from S; -   Ar¹ can be selected from unsubstituted C₆ to C₁₂ heteroaryl; -   Ar² can be selected from unsubstituted C₆ to C₁₂ arylene; -   Ar³ can be selected from unsubstituted C₆ to C₁₂ heteroaryl.

According to another embodiment, formula 1 may comprises at least about 5 to about 16 C₆ aryl rings.

According to another embodiment, formula 1 may comprises at least about 5 to about 16 C₆ aryl rings and at least about 1 to about 5 six-member hetero aryl rings, wherein at least one six-member hetero aryl ring is a triazine and the hetero atoms can be individually selected from N, O, S.

According to an aspect the compound of formula 1 can be used as a matrix material for a dopant material.

According to an aspect the layer material can be an organic semiconductor layer, which is used for an organic electronic device. For example, the organic electronic device can be an OLED or there like.

The compounds represented by formula 1 have strong electron transport characteristics to increase charge mobility and/or stability and thereby to improve luminance efficiency, voltage characteristics, and/or lifetime characteristics.

The compounds represented by formula 1 have high electron mobility and a low operating voltage.

The compounds represented by formula 1 and an organic semiconductor layer consisting or comprising of a compound of formula 1 may be non-emissive.

In the context of the present specification the term “essentially non-emissive” or “non-emitting” means that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5% relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about <780 nm.

Preferably, the organic semiconductor layer comprising the compound of formula 1 is essentially non-emissive or non-emitting.

The term “free of”, “does not contain”, “does not comprise” does not exclude impurities which may be present in the compounds prior to deposition. Impurities have no technical effect with respect to the object achieved by the present invention.

The operating voltage, also named U, is measured in Volt (V) at 10 milliAmpere per square centimeter (mA/cm2).

The candela per Ampere efficiency, also named cd/A efficiency, is measured in candela per ampere at 10 milliAmpere per square centimeter (mA/cm2).

The external quantum efficiency, also named EQE, is measured in percent (%).

The color space is described by coordinates CIE-x and CIE-y (International Commission on Illumination 1931). For blue emission the CIE-y is of particular importance. A smaller CIE-y denotes a deeper blue color.

The highest occupied molecular orbital, also named HOMO, and lowest unoccupied molecular orbital, also named LUMO, are measured in electron volt (eV).

The term “OLED”, “organic light emitting diode”, “organic light emitting device”, “organic optoelectronic device” and “organic light-emitting diode” are simultaneously used and have the same meaning.

The term “transition metal” means and comprises any element in the d-block of the periodic table, which comprises groups 3 to 12 elements on the periodic table.

The term “group III to VI metal” means and comprises any metal in groups III to VI of the periodic table.

As used herein, “weight percent”, “wt.-%”, “percent by weight”, “% by weight”, and variations thereof refer to a composition, component, substance or agent as the weight of that composition, component, substance or agent of the respective electron transport layer divided by the total weight of the composition thereof and multiplied by 100. It is understood that the total weight percent amount of all components, substances or agents of the respective electron transport layer are selected such that it does not exceed 100 wt.-%.

As used herein, “volume percent”, “vol.-%”, “percent by volume”, “% by volume”, and variations thereof refer to an elemental metal, a composition, component, substance or agent as the volume of that elemental metal, component, substance or agent of the respective electron transport layer divided by the total volume of the respective electron transport layer thereof and multiplied by 100. It is understood that the total volume percent amount of all elemental metal, components, substances or agents of the respective cathode electrode layer are selected such that it does not exceed 100 vol.-%.

All numeric values are herein assumed to be modified by the term “about”, whether or not explicitly indicated. As used herein, the term “about” refers to variation in the numerical quantity that can occur.

Whether or not modified by the term “about”, the claims include equivalents to the quantities.

It should be noted that, as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise.

It should be noted that, as used in this specification and the appended claims, “*” if not otherwise defined indicates the chemical bonding position.

The anode electrode and cathode electrode may be described as anode electrode/cathode electrode or anode electrode/cathode electrode or anode electrode layer/cathode electrode layer.

According to another aspect, an organic optoelectronic device comprises an anode layer and a cathode layer facing each other and at least one organic semiconductor layer between the anode layer and the cathode layer, wherein the organic semiconductor layer comprises or consists of the compound of formula 1.

According to yet another aspect, a display device comprising the organic electronic device, which can be an organic optoelectronic device, is provided.

In the present specification, when a definition is not otherwise provided, an “alkyl group” may refer to an aliphatic hydrocarbon group. The alkyl group may refer to “a saturated alkyl group” without any double bond or triple bond. The alkyl group may be a linear, cyclic or branched alkyl group.

The alkyl group may be a C₁ to C₁₆ alkyl group, or preferably a C₁ to C₁₂ alkyl group. More specifically, the alkyl group may be a C₁ to C₁₄ alkyl group, or preferably a C₁ to C₁₀ alkyl group or a C₁ to C₆ alkyl group. For example, a C₁ to C₄ alkyl group comprises 1 to 4 carbons in alkyl chain, and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.

Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

In the present specification, when a definition is not otherwise provided, R² can be independently selected from H, C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl.

In the present specification “arylene group” may refer to a group comprising at least one hydrocarbon aromatic moiety, and all the elements of the hydrocarbon aromatic moiety may have p-orbitals which form conjugation, for example a phenyl group, a naphtyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a fluorenyl group and the like.

The arylene group may include a monocyclic, polycyclic or fused ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.

The term “heteroarylene” may refer to aromatic heterocycles with at least one heteroatom, and all the elements of the hydrocarbon heteroaromatic moiety may have p-orbitals which form conjugation. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably from N, O and S.

A heteroarylene ring may comprise at least 1 to 3 heteroatoms. Preferably a heteroarylene ring may comprise at least 1 to 3 heteroatoms individually selected from N, S and/or 0.

Further preferred in addition to the triazine group of formula 1 at least one additional heteroaryl/ene ring may comprise at least 1 to 3 N-atoms, or at least 1 to 2-N atoms or at least one N-atom.

The term “heteroarylene” as used herewith shall encompass dibenzofurane, dibenzothiopene, pyridine, quinoline, quinazoline, pyrimidine, triazine, benzimidazole, benzothiazole, benzoxazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenoxazine, benzoacridine, dibenzoacridine and the like.

In the present specification, the single bond refers to a direct bond.

In the present specification, when a definition is not otherwise provided, Ar¹ can be independently selected from substituted or unsubstituted C₆-C₂₄ aryl or C₃-C₃₆ heteroaryl, wherein the substituents of C₆-C₂₄ aryl or C₃-C₃₆ heteroaryl are independently selected from linear C₁₋₁₆ alkyl, branched C₃₋₁₆ alkyl, CN.

Preferably Ar¹ can be independently selected from substituted or unsubstituted C₆-C₁₈ aryl or C₃-C₁₇ heteroaryl, wherein the substituents of C₆-C₁₈ aryl or C₃-C₁₇ heteroaryl are independently selected from linear C₁₋₁₆ alkyl, branched C₃₋₁₀ alkyl, CN.

Further preferred, Ar¹ can be independently selected from substituted or unsubstituted C₆-C₁₂ aryl or C₄-C₁₁ heteroaryl, wherein the substituents of C₆-C₁₂ aryl or C₅-C₁₁ heteroaryl are independently selected from linear C₁₋₃ alkyl, branched C₃₋₅ alkyl.

In addition preferred, Ar¹ can be independently selected from unsubstituted C₆-C₁₂ aryl or C₃-C₁₁ heteroaryl, C₄-C₁₁ heteroaryl or C₅-C₁₁ heteroaryl.

In the present specification, when a definition is not otherwise provided, Ar² can be independently selected from C₁ to C₁₆ alkylene, substituted or unsubstituted C₆₋₃₆ arylene; wherein the substituents of the C₆₋₃₆ arylene are independently selected from C₁-C₁₆ alkyl, CN.

According to another preferred embodiment the compound according to formula 1 may comprise:

-   -   at least 7 to 25 aromatic rings, preferably at least 8 to 22         aromatic rings, further preferred at least 9 to 20 aromatic         rings, in addition preferred at least 10 to 15 aromatic rings         and more preferred at least 10 to 14 aromatic rings; wherein     -   at least 2 to 5, preferably 3 to 4 or 2 to 3, are heteroaromatic         rings.

According to one embodiment the compound according to formula 1:

-   -   comprises at least about 8 to about 20 aromatic rings,         preferably at least about 9 to about 18 aromatic rings, further         preferred at least about 10 to about 16 aromatic rings, in         addition preferred at least about 11 to about 15 aromatic rings         and more preferred at least about 10 to about 14 aromatic rings;         and/or     -   the compound of formula 1 comprises at least about 2 to about 6,         preferably about 3 to about 5 or about 2 to about 4, hetero         aromatic rings, wherein the hetero atoms can be selected from N,         O, S; and/or     -   comprises at least one fluorene ring and at least one         hetero-fluorene ring, wherein the hetero atoms can be selected         from N, O, S; and/or     -   comprises at least one triazine ring, and preferably at least         two triazine rings.

According to one preferred embodiment the compound according to formula 1 may comprises at least about 8 to about 20 aromatic rings, preferably at least about 9 to 18 aromatic rings, further preferred at least 10 to about 16 aromatic rings, in addition preferred at least 8 to 15 aromatic rings and more preferred at least about 10 to about 14 aromatic rings, wherein at least one of the aromatic rings is an unsubstituted five member ring and at least one of the aromatic rings is a five member hetero-ring.

According to one preferred embodiment the compound according to formula 1 may comprises at least about 8 to about 20 aromatic rings, preferably at least about 9 to 18 aromatic rings, further preferred at least 10 to about 16 aromatic rings, in addition preferred at least 8 to 15 aromatic rings and more preferred at least about 10 to about 14 aromatic rings, wherein at least one of the aromatic rings is an unsubstituted five member ring and at least one of the aromatic rings is a five member hetero-ring.

According to a further preferred embodiment the compound of formula 1 comprises at least 2 to 7, preferably 2 to 5, or 2 to 3 hetero aromatic rings.

According to a further preferred embodiment the compound of formula 1 comprises at least 2 to 7, preferably 2 to 5, or 2 to 3 hetero aromatic rings, wherein at least one of the aromatic rings is a five member hetero aromatic ring.

According to a further preferred embodiment the compound of formula 1 comprises at least 3 to 7, preferably 3 to 6, or 3 to 5 hetero aromatic rings, wherein at least two of the hetero aromatic rings are five member hetero-aromatic-ring.

According to one embodiment the compound according to formula 1 may comprise at least 6 to 12 non-hetero aromatic rings and 2 to 3 hetero aromatic rings.

According to one preferred embodiment the compound according to formula 1 may comprise at least 7 to 12 non-hetero aromatic rings and 2 to 5 hetero aromatic rings.

According to one preferred embodiment the compound according to formula 1 may comprise at least 7 to 11 non-hetero aromatic rings and 2 to 3 hetero aromatic rings.

The term “C₆-arylene ring” means single C₆-arylene rings and C₆-arylene rings which form condensed ring systems. For example, a naphthalene group would be counted as two C₆-arylene rings.

According to another embodiment of formula 1, wherein for Ar¹ and/or Ar³ at least one heteroarylene group is selected from dibenzofurane, dibenzothiophene, triazine, quinoline, quinazoline, benzimidazole, benzothiazole, benzoxazole, benzo[4,5]thieno[3,2-d]pyrimidine, acridine, benzoacridine, dibenzoacridine, pyrimidine and pyridine, and is preferably selected from pyridine, quinoline, dibenzofurane or dibenzothiophene.

According to another embodiment, Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl and Ar³ is selected from dibenzofurane, dibenzothiophene, triazine, quinoline, quinazoline, benzimidazole, benzothiazole, benzoxazole, benzo[4,5]thieno[3,2-d]pyrimidine, acridine, benzoacridine, dibenzoacridine, pyrimidine and is preferably selected from quinoline, dibenzofurane or dibenzothiophene.

According to another embodiment the compound of formula 1 may have a glass transition temperature Tg of about ≥115° C. and about ≤380° C., preferably about ≥120° C. and about ≤350° C., further preferred about ≥125° C. and about ≤320° C., in addition preferred about ≥125° C. and about ≤200° C. and also preferred about ≥125° C. and about ≤180° C.

According to another embodiment the compound of formula 1 may have a glass transition temperature Tg of about ≥125° C. and about ≤150° C.

The glass transition temperature is measured under nitrogen and using a heating rate of 10 K per min in a Mettler Toledo DSC 822e differential scanning calorimeter as described in DIN EN ISO 11357, published in March 2010.

Room temperature, also named ambient temperature, is 23° C.

Surprisingly, it was found that the compounds of formula 1 and the inventive organic electronic devices solve the problem underlying the present invention by being superior over the organic electroluminescent devices and compounds known in the art, in particular with respect to cd/A efficiency, also referred to as current efficiency and to lifetime. At the same time the operating voltage is kept at a similar or even improved level which is important for reducing power consumption and increasing battery life, for example of a mobile display device. High cd/A efficiency is important for high efficiency and thereby increased battery life of a mobile device, for example a mobile display device. Long lifetime is important for the longevity of a device.

The inventors have surprisingly found that particular good performance can be achieved when using the organic electroluminescent device as a fluorescent blue device.

The specific arrangements mentioned herein as preferred were found to be particularly advantageous.

Likewise, some compounds falling within the scope of the broadest definition of the present invention have surprisingly be found to be particularly well performing with respect to the mentioned property of cd/A efficiency and lifetime. These compounds are discussed herein to be particularly preferred.

Further an organic optoelectronic device having high efficiency and/or long lifetime may be realized.

According to one embodiment, the compound according to formula 1, may have the formula 1a:

According to another embodiment, the compound according to formula 1, may have the formula 1a:

-   wherein -   X is selected from O or S; -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; -   Ar² is selected from C₁ to C₁₆ alkylene, substituted or     unsubstituted C₆ to C₃₆ arylene; -   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;     and -   wherein     -   substituted C₆ to C₂₄ aryl of Ar¹ or substituted C₃ to C₃₆         heteroaryl of Ar¹ is mono or di-substituted; and -   wherein     -   substituted C₆ to C₃₆ aryl of Ar³ or substituted C₃ to C₃₆         heteroaryl of Ar³ is mono or di-substituted.

According to another embodiment of the compound according to formula 1 may have the formula 1a:

-   wherein -   X is selected from O; -   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or substituted or     unsubstituted C₃ to C₃₆ heteroaryl; -   Ar² is selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ is selected from unsubstituted C₆ to C₃₆ aryl or unsubstituted     C₃ to C₃₆ heteroaryl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl; -   Ar² is selected from unsubstituted C₆ to C₃₆ arylene; -   Ar³ is selected from unsubstituted C₆ to C₃₆ aryl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is substituted or unsubstituted C₆ to C₁₂ aryl, or substituted     or unsubstituted C₃ to C₁₈ heteroaryl, preferably phenyl or biphenyl     and in addition preferred phenyl, wherein     -   the substituents of the substituted C₆ to C₁₂ aryl and         substituted C₃ to C₁₈ heteroaryl are selected from C₁ to C₁₀         alkyl or CN, preferably from C₁ to C₆ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar² is substituted or unsubstituted C₆ to C₁₃ arylene, more     preferred phenylene or biphenylene and in addition preferred     phenylene, wherein     -   the substituents of the substituted C₆ to C₁₂ arylene are         selected from C₁ to C₁₀ alkyl or CN, preferably from C₁ to C₆         alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar³ is substituted or unsubstituted C₆ to C₂₄ aryl, preferably     phenyl or biphenyl and in addition preferred phenyl, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl are selected         from C₁ to C₁₀ alkyl or CN, preferably from C₁ to C₆ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar¹ is selected from substituted or unsubstituted annelated C₆ to     C₂₄ aryl or substituted or unsubstituted annelated C₃ to C₃₆     heteroaryl, wherein     -   the substituents of the substituted annelated C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ annelated heteroaryl are selected from C₁         to C₁₆ alkyl, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl or CN,         preferably from C₁ to C₁₆ alkyl, and preferably C₁ to C₃ alkyl.

According to another embodiment of formula 1 and/or formula 1a, wherein

-   Ar³ is selected from unsubstituted C₆ to C₂₄ aryl, preferably phenyl     or biphenyl and in addition preferred phenyl; and -   Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ to C₁₆ alkyl     substituted C₆ to C₂₄ aryl.

According to another embodiment of formula 1 and/or formula 1a, wherein Ar¹ and A³ are selected different.

According to another embodiment of formula 1 and/or formula 1a,

-   wherein Ar¹ and A³ are independently selected from B1 to B53: -   wherein -   a) B1 to B6 are substituted or unsubstituted non-heteroaryl groups:

-   b) B7 to B16 are substituted or unsubstituted annelated     non-heteroaryl groups:

-   c) B17 to B25 are dibenzofurane/dibenzothiophene group:

-   d) B26 to B28 are unsubstituted pyridine groups:

-   e) B29 to B46 are unsubstituted or substituted hetero arylene     groups:

-   f) B47 to B48 unsubstituted annelated hetero arylene groups:

-   g) B49 and B50 are nitrile substituted phenyl groups

-   h) B51 to B53 are nitrile substituted biphenyl groups

-   wherein     -   the substituent R² is independently selected from H, C₁ to C₁₆         alkyl, C₆ to C₁₈ aryl.

According to another embodiment of formula 1 and/or formula 1a, Ar¹ and Ar³ are selected from B1 to B25 and B51 to B53, preferably B1 to B25.

According to another embodiment of formula 1 and/or formula 1a, Ar¹ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment of formula 1 and/or formula 1a, Ar³ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B6, more preferred B1.

According to another embodiment, in compound of formula 1 or 1a,

-   -   Ar¹ is selected from B1 to B25 and B51 to B53, preferably is         selected from B1 to B25, also preferred is selected from B2, B5,         B8, B11, B12, B13, B14, B15, also preferred is selected from B2,         B5, B8, B11, B12, B13; and     -   Ar³ is selected from B1 to B6, preferably is selected from B1.

According to one embodiment, the compound according to formula 1 may have the formula 1b:

According to one embodiment, the compound according to formula 1 may have the formula 1b:

-   wherein -   X is selected from O or S; -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; -   Ar² is selected from C₁ to C₁₆ alkylene or is selected from     unsubstituted arylene (C7) to (C11):

further preferred Ar² is selected from unsubstituted arylene C₇, C₉, C₁₀ or C₁₁, more preferred Ar² is selected from unsubstituted arylene C₇;

-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;     and -   wherein     -   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃ to         C₃₆ heteroaryl is mono or di-substituted, wherein         -   the substituents of the substituted C₆ to C₂₄ aryl and             substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆             alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to             C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆             to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN; and -   wherein     -   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to         C₃₆ heteroaryl is mono or di-substituted, wherein         -   the substituents of the substituted C₆ to C₃₆ aryl and             substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆             alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to             C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆             to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN.

According to another embodiment, in compound of formula 1b, Ar¹ and Ar³ are selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25.

According to another embodiment, in compound of formula 1b, Ar¹ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment, in compound of formula 1b, Ar³ is selected from B1 to B25 and B51 to B53.

According to another embodiment, in compound of formula 1b, Ar³ is selected from phenyl and Ar¹ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to one embodiment, the compound according to formula 1 may have the formula 1c:

According to one embodiment, the compound according to formula 1 may have the formula 1c:

-   wherein -   X is selected from O or S; -   Ar¹ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₂₄ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; -   Ar² is selected from C₁ to C₁₆ alkylene or is selected from     unsubstituted arylene (C7) to (C11):

further preferred Ar² is selected from unsubstituted arylene C₇, C₉, C₁₀ or C₁₁, more preferred Ar² is selected from unsubstituted arylene C₇;

-   Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted     C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl;     and -   wherein -   Ar¹ of substituted C₆ to C₂₄ aryl or Ar¹ of substituted C₃ to C₃₆     heteroaryl is mono or di-substituted, wherein     -   the substituents of the substituted C₆ to C₂₄ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆         alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈         aryl, C₃ to C₂₅ heteroaryl, F or CN; and -   wherein -   Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to C₃₆     heteroaryl is mono or di-substituted, wherein     -   the substituents of the substituted C₆ to C₃₆ aryl and         substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆         alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆         alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈         aryl, C₃ to C₂₅ heteroaryl, F or CN.

According to another embodiment, in compound of formula 1c, Ar¹ and Ar³ are selected from B1 to B25 and B51 to B53, preferably are selected from B1 to B25.

According to another embodiment, in compound of formula 1c, Ar¹ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to another embodiment, in compound of formula 1c, Ar³ is selected from B1 to B25 and B51 to B53.

According to another embodiment, in compound of formula 1c, Ar³ is selected from phenyl and Ar¹ is selected from B1 to B25 and B51 to B53, preferably is selected from B1 to B25, also preferred is selected from B2, B5, B8, B11, B12, B13, B14, B15, also preferred is selected from B2, B5, B8, B11, B12, B13.

According to one embodiment of the compound according to formula 1, Ar² may be selected from C₁ to C₁₈:

and preferably Ar² is selected from C₆ to C₁₄, further preferred Ar² is selected from C₇ to C₁₁ and more preferred from C₇.

According to another embodiment the compound of formula 1 can be selected from a compound of D1 to D11:

Anode

A material for the anode may be a metal or a metal oxide, or an organic material, preferably a material with work function above about 4.8 eV, more preferably above about 5.1 eV, most preferably above about 5.3 eV. Preferred metals are noble metals like Pt, Au or Ag, preferred metal oxides are transparent metal oxides like ITO or IZO which may be advantageously used in bottom-emitting OLEDs having a reflective cathode.

In devices comprising a transparent metal oxide anode or a reflective metal anode, the anode may have a thickness from about 50 nm to about 100 nm, whereas semitransparent metal anodes may be as thin as from about 5 nm to about 15 nm, and non-transparent metal anodes may have a thickness from about 15 nm to about 150 nm.

Hole Injection Layer (HIL)

The hole injection layer may improve interface properties between the anode and an organic material used for the hole transport layer, and is applied on a non-planarized anode and thus may planarize the surface of the anode. For example, the hole injection layer may include a material having a median value of the energy level of its highest occupied molecular orbital (HOMO) between the work function of the anode material and the energy level of the HOMO of the hole transport layer, in order to adjust a difference between the work function of the anode and the energy level of the HOMO of the hole transport layer.

When the hole transport region comprises a hole injection layer 36, the hole injection layer may be formed on the anode by any of a variety of methods, for example, vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) method, or the like.

When hole injection layer is formed using vacuum deposition, vacuum deposition conditions may vary depending on the material that is used to form the hole injection layer, and the desired structure and thermal properties of the hole injection layer to be formed and for example, vacuum deposition may be performed at a temperature of about 100° C. to about 500° C., a pressure of about 10⁻⁶ Pa to about 10⁻¹ Pa, and a deposition rate of about 0.1 to about 10 nm/sec, but the deposition conditions are not limited thereto.

When the hole injection layer is formed using spin coating, the coating conditions may vary depending on the material that is used to form the hole injection layer, and the desired structure and thermal properties of the hole injection layer to be formed. For example, the coating rate may be in the range of about 2000 rpm to about 5000 rpm, and a temperature at which heat treatment is performed to remove a solvent after coating may be in a range of about 80° C. to about 200° C., but the coating conditions are not limited thereto.

The hole injection layer may further comprise a p-dopant to improve conductivity and/or hole injection from the anode.

p-Dopant

In another aspect, the p-dopant may be homogeneously dispersed in the hole injection layer.

In another aspect, the p-dopant may be present in the hole injection layer in a higher concentration closer to the anode and in a lower concentration closer to the cathode.

The p-dopant may be one of a quinone derivative or a radialene compound but not limited thereto. Non-limiting examples of the p-dopant are quinone derivatives such as tetracyanoquinonedimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), 4,4′,4″-((1E,1′E,1″E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))-tris(2,3,5,6-tetrafluorobenzonitrile).

Hole Transport Layer (HTL)

Conditions for forming the hole transport layer and the electron blocking layer may be defined based on the above-described formation conditions for the hole injection layer.

A thickness of the hole transport part of the charge transport region may be from about 10 nm to about 1000 nm, for example, about 10 nm to about 100 nm. When the hole transport part of the charge transport region comprises the hole injection layer and the hole transport layer, a thickness of the hole injection layer may be from about 10 nm to about 1000 nm, for example about 10 nm to about 100 nm and a thickness of the hole transport layer may be from about 5 nm to about 200 nm, for example about 10 nm to about 150 nm. When the thicknesses of the hole transport part of the charge transport region, the HIL, and the HTL are within these ranges, satisfactory hole transport characteristics may be obtained without a substantial increase in operating voltage.

Hole transport matrix materials used in the hole transport region are not particularly limited. Preferred are covalent compounds comprising a conjugated system of at least 6 delocalized electrons, preferably organic compounds comprising at least one aromatic ring, more preferably organic compounds comprising at least two aromatic rings, even more preferably organic compounds comprising at least three aromatic rings, most preferably organic compounds comprising at least four aromatic rings. Typical examples of hole transport matrix materials which are widely used in hole transport layers are polycyclic aromatic hydrocarbons, triarylene amine compounds and heterocyclic aromatic compounds. Suitable ranges of frontier orbital energy levels of hole transport matrices useful in various layer of the hole transport region are well-known. In terms of the redox potential of the redox couple HTL matrix/cation radical of the HTL matrix, the preferred values (if measured for example by cyclic voltammetry against ferrocene/ferrocenium redox couple as reference) may be in the range 0.0-1.0 V, more preferably in the range 0.2-0.7 V, even more preferably in the range 0.3-0.5 V.

Buffer Layer

The hole transport part of the charge transport region may further include a buffer layer.

Buffer layer that can be suitable used are disclosed in U.S. Pat. Nos. 6,140,763, 6,614,176 and in US2016/248022.

The buffer layer may compensate for an optical resonance distance of light according to a wavelength of the light emitted from the EML, and thus may increase efficiency.

Emission Layer (EML)

The emission layer may be formed on the hole transport region by using vacuum deposition, spin coating, casting, LB method, or the like. When the emission layer is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the hole injection layer, though the conditions for the deposition and coating may vary depending on the material that is used to form the emission layer. The emission layer may include an emitter host (EML host) and an emitter dopant (further only emitter).

A thickness of the emission layer may be about 100 Å to about 1000 Å, for example about 200 Å to about 600 Å. When the thickness of the emission layer is within these ranges, the emission layer may have improved emission characteristics without a substantial increase in operating voltage.

Emitter Host

According to another embodiment, the emission layer comprises compound of formula 1 as emitter host.

The emitter host compound has at least three aromatic rings, which are independently selected from carbocyclic rings and heterocyclic rings.

Other compounds that can be used as the emitter host is an anthracene matrix compound represented by formula 400 below:

In formula 400, Ar₁₁₁ and Ar₁₁₂ may be each independently a substituted or unsubstituted C₆-C₆₀ arylene group; Ar₁₁₃ to Ar₁₁₆ may be each independently a substituted or unsubstituted C₁-C₁₀ alkyl group or a substituted or unsubstituted C₆-C₆₀ arylene group; and g, h, i, and j may be each independently an integer from 0 to 4.

In some embodiments, Ar₁₁₁ and Ar₁₁₂ in formula 400 may be each independently one of a phenylene group, a naphthalene group, a phenanthrenylene group, or a pyrenylene group; or a phenylene group, a naphthalene group, a phenanthrenylene group, a fluorenyl group, or a pyrenylene group, each substituted with at least one of a phenyl group, a naphthyl group, or an anthryl group.

In formula 400, g, h, i, and j may be each independently an integer of 0, 1, or 2.

In formula 400, Ar₁₁₃ to Ar₁₁₆ may be each independently one of

-   -   a C₁-C₁₀ alkyl group substituted with at least one of a phenyl         group, a naphthyl group, or an anthryl group;     -   a phenyl group, a naphthyl group, an anthryl group, a pyrenyl         group, a phenanthrenyl group, or a fluorenyl group;     -   a phenyl group, a naphthyl group, an anthryl group, a pyrenyl         group, a phenanthrenyl group, or a fluorenyl group, each         substituted with at least one of a deuterium atom, a halogen         atom, a hydroxyl group, a cyano group, a nitro group, an amino         group, an amidino group, a hydrazine group, a hydrazone group, a         carboxyl group or a salt thereof,     -   a sulfonic acid group or a salt thereof, a phosphoric acid group         or a salt thereof,     -   a C₁-C₆₀ alkyl group, a C₂-C₆₀ alkenyl group, a C₂-C₆₀ alkynyl         group, a C₁-C₆₀ alkoxy group, a phenyl group, a naphthyl group,         an anthryl group, a pyrenyl group, a phenanthrenyl group, or     -   a fluorenyl group

or

-   -   formulas 7 or 8

Wherein in the formulas 7 and 8, X is selected form an oxygen atom and a sulfur atom, but embodiments of the invention are not limited thereto.

In the formula 7, any one of R₁₁ to R₁₄ is used for bonding to Ar₁₁₁. R₁₁ to R₁₄ that are not used for bonding to Ar₁₁₁ and R₁₅ to R₂₀ are the same as R₁ to R₈.

In the formula 8, any one of R₂₁ to R₂₄ is used for bonding to Ar₁₁₁. R₂₁ to R₂₄ that are not used for bonding to Ar₁₁₁ and R₂₅ to R₃₀ are the same as R₁ to R₈.

Preferably, the EML host comprises between one and three heteroatoms selected from the group consisting of N, O or S. More preferred the EML host comprises one heteroatom selected from S or O.

Emitter Dopant

The dopant is mixed in a small amount to cause light emission, and may be generally a material such as a metal complex that emits light by multiple excitation into a triplet or more. The dopant may be, for example an inorganic, organic, or organic/inorganic compound, and one or more kinds thereof may be used.

The emitter may be a red, green, or blue emitter.

The dopant may be a fluorescent dopant, for example ter-fluorene, the structures are shown below. 4.4′-bis(4-diphenyl amiostyryl)biphenyl (DPAVBI, 2,5,8,11-tetra-tert-butyl perylene (TBPe), and Compound 8 below are examples of fluorescent blue dopants.

The dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal compound comprising Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example a compound represented by formula Z, but is not limited thereto: J₂MX  (Z).

In formula Z, M is a metal, and J and X are the same or different, and are a ligand to form a complex compound with M.

The M may be, for example Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof, and the J and X may be, for example a bidendate ligand.

Electron Transport Layer (ETL)

According to another embodiment, the organic semiconductor layer that comprises a compound of formula 1 is an electron transport layer. In another embodiment the electron transport layer may consist of a compound of formula 1.

For example, an organic light emitting diode according to an embodiment of the present invention comprises at least one electron transport layer, and in this case, the electron transport layer comprises a compound of formula 1, or preferably of at least one compound of formulae D1 to D11.

In another embodiment, the organic electronic device comprises an electron transport region of a stack of organic layers formed by two or more electron transport layers, wherein at least one electron transport layer comprises a compound of formula 1.

The electron transport layer may include one or two or more different electron transport compounds.

According to another embodiment, a second electron transport layer comprises at least one compound of formula 1 according to the invention and a first electron transport layer comprises a matrix compound, which is selected different to the compound of formula 1 according to the invention, and may be selected from:

-   -   an anthracene based compound or a hetero substituted anthracene         based compound, preferably         2-(4-(9,10-di(naphthalen-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole         and/or         N4,N4″-di(naphthalen-1-yl)-N4,N4″-diphenyl-[1,1′:4′,1″-terphenyl]-4,4″-diamine.

According to another embodiment, a first electron transport layer comprises at least one compound of formula 1 according to the invention and a second electron transport layer comprises a matrix compound, which is selected different to the compound of formula 1 according to the invention, and may be selected from:

-   -   a phosphine oxide based compound, preferably         (3-(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide         and/or phenyl bis(3-(pyren-1-yl)phenyl)phosphine oxide and/or         3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphepine-3-oxide;         or     -   a substituted phenanthroline compound, preferably         2,4,7,9-tetraphenyl-1,10-phenanthroline or         2,9-di(biphenyl-4-yl)-4,7-diphenyl-1,10-phenanthroline.

According to another embodiment a first electron transport layer comprises at least one compound of formula 1 according to the invention and a second electron transport layer comprises a matrix compound, which is selected different to the compound of formula 1 according to the invention, and may be selected from a phosphine oxide based compound, preferably (3-(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide and/or phenyl bis(3-(pyren-1-yl)phenyl)phosphine oxide and/or 3-Phenyl-3H-benzo[b]dinaphtho[2,1-d:1′,2′-f]phosphepine-3-oxide.

According to another embodiment, a first and a second electron transport layers comprise a compound of formula 1, wherein the compound of formula 1 is not selected the same.

The thickness of the first electron transport layer may be from about 0.5 nm to about 100 nm, for example about 2 nm to about 40 nm. When the thickness of the first electron transport layer is within these ranges, the first electron transport layer may have improved electron transport ability without a substantial increase in operating voltage.

A thickness of an optional second electron transport layer may be about 1 nm to about 100 nm, for example about 2 nm to about 20 nm. When the thickness of the electron transport layer is within these ranges, the electron transport layer may have satisfactory electron transporting ability without a substantial increase in operating voltage.

The electron transport layer may further comprise an alkali halide and/or alkali organic complex.

According to another embodiment, the first and second electron transport layers comprise a compound of formula 1, wherein the second electron transport layer further comprises an alkali halide and/or alkali organic complex.

Alkali Halide

Alkali halides, also known as alkali metal halides, are the family of inorganic compounds with the chemical formula MX, where M is an alkali metal and X is a halogen.

M can be selected from Li, Na, Potassium, Rubidium and Cesium.

X can be selected from F, Cl, Br and J.

According to various embodiments of the present invention a lithium halide may be preferred. The lithium halide can be selected from the group comprising LiF, LiCl, LiBr and LiJ. However, most preferred is LiF.

The alkali halide is essentially non-emissive or non-emissive.

Alkali Organic Complex

The alkali organic complex comprises an alkali metal and at least one organic ligand. The alkali metal is preferably selected from lithium.

According to various embodiments of the present invention the organic ligand of the lithium organic complex is a quinolate, a borate, a phenolate, a pyridinolate or a Schiff base ligand;

-   -   preferably the lithium quinolate complex has the formula III, IV         or V:

-   wherein     -   A₁ to A₆ are same or independently selected from CH, CR, N and         O;     -   R is same or independently selected from hydrogen, halogen,         alkyl or arylene or heteroarylene with 1 to 20 carbon atoms; and         more preferred A1 to A6 are CH;     -   preferably the borate based organic ligand is a         tetra(1H-pyrazol-1-yl)borate;     -   preferably the phenolate is a 2-(pyridin-2-yl)phenolate, a         2-(diphenylphosphoryl)phenolate, an imidazol phenolates, or         2-(pyridin-2-yl)phenolate and more preferred         2-(l-phenyl-1H-benzo[d]imidazol-2-yl)phenolate;     -   preferably the pyridinolate is a         2-(diphenylphosphoryl)pyridin-3-olate.

According to various embodiments of the present invention the organic ligand of the alkali organic complex, preferably of a lithium organic complex, can be a quinolate. Quinolates that can be suitable used are disclosed in WO 2013079217 A1 and incorporated by reference.

According to various embodiments of the present invention the organic ligand of the lithium organic complex can be a borate based organic ligand, Preferably the lithium organic complex is a lithium tetra(1H-pyrazol-1-yl)borate. Borate based organic ligands that can be suitable used are disclosed in WO 2013079676 A1 and incorporated by reference.

According to various embodiments of the present invention the organic ligand of the lithium organic complex can be a phenolate ligand, Preferably the lithium organic complex is a lithium 2-(diphenylphosphoryl)phenolate. Phenolate ligands that can be suitable used are disclosed in WO 2013079678 A1 and incorporated by reference.

Further, phenolate ligands can be selected from the group of pyridinolate, preferably 2-(diphenylphosphoryl)pyridin-3-olate. Pyridine phenolate ligands that can be suitable used are disclosed in JP 2008195623 and incorporated by reference.

In addition, phenolate ligands can be selected from the group of imidazol phenolates, preferably 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate. Imidazol phenolate ligands that can be suitable used are disclosed in JP 2001291593 and incorporated by reference.

Also, phenolate ligands can be selected from the group of oxazol phenolates, preferably 2-(benzo[d]oxazol-2-yl)phenolate. Oxazol phenolate ligands that can be suitable used are disclosed in US 20030165711 and incorporated by reference.

The alkali organic complex may be essentially non-emissive.

Electron Injection Layer (EIL)

According to another aspect of the invention, the organic electroluminescent device may further comprise an electron injection layer between the electron transport layer (first-ETL) and the cathode.

The electron injection layer (EIL) may facilitate injection of electrons from the cathode.

According to another aspect of the invention, the electron injection layer comprises:

-   (i) an electropositive metal selected from alkali metals, alkaline     earth metals and rare earth metals in substantially elemental form,     preferably selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Eu and     Yb, more preferably from Li, Na, Mg, Ca, Sr and Yb, even more     preferably from Li and Yb, most preferably Yb; and/or -   (ii) an alkali metal complex and/or alkali metal salt, preferably     the Li complex and/or salt, more preferably a Li quinolinolate, even     more preferably a lithium 8-hydroxyquinolinolate, most preferably     the alkali metal salt and/or complex of the second electron     transport layer (second-ETL) is identical with the alkali metal salt     and/or complex of the injection layer. The electron injection layer     may include at least one selected from LiF, NaCl, CsF, Li₂O, and     BaO.

A thickness of the EIL may be from about 0.1 nm to about 10 nm, or about 0.3 nm to about 9 nm. When the thickness of the electron injection layer is within these ranges, the electron injection layer may have satisfactory electron injection ability without a substantial increase in operating voltage.

The electron injection layer may comprise a compound of formula 1.

Cathode

A material for the cathode may be a metal, an alloy, or an electrically conductive compound that have a low work function, or a combination thereof. Specific examples of the material for the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), silver (Ag) etc. In order to manufacture a top-emission light-emitting device having a reflective anode deposited on a substrate, the cathode may be formed as a light-transmissive electrode from, for example, indium tin oxide (ITO), indium zinc oxide (IZO) or silver (Ag).

In devices comprising a transparent metal oxide cathode or a reflective metal cathode, the cathode may have a thickness from about 50 nm to about 100 nm, whereas semitransparent metal cathodes may be as thin as from about 5 nm to about 15 nm.

Substrate

A substrate may be further disposed under the anode or on the cathode. The substrate may be a substrate that is used in a general organic light emitting diode and may be a glass substrate or a transparent plastic substrate with strong mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.

Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples.

DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings, of which:

FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer, one electron transport layer and an electron injection layer;

FIG. 2 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and two electron transport layers;

FIG. 3 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention with an emission layer and three electron transport layers;

FIG. 4 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and one electron transport layer;

FIG. 5 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention with an emission layer and two electron transport layers;

FIG. 6 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention with an emission layer and three electron transport layers.

Reference will now be made in detail to the exemplary aspects, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The exemplary embodiments are described below, in order to explain the aspects, by referring to the figures.

Herein, when a first element is referred to as being formed or disposed “on” a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed “directly on” a second element, no other elements are disposed there between.

The term “contacting sandwiched” refers to an arrangement of three layers whereby the layer in the middle is in direct contact with the two adjacent layers.

The organic light emitting diodes according to an embodiment of the present invention may include a hole transport region; an emission layer; and a first electron transport layer comprising a compound according to formula 1.

FIG. 1 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150, an electron transport layer (ETL) 161 comprising a compound of formula 1 and an electron injection layer 180, whereby the first electron transport layer 161 is disposed directly on the emission layer 150 and the electron injection layer 180 is disposed directly on the first electron transport layer 161.

FIG. 2 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150 and an electron transport layer stack (ETL) 160 comprising a first electron transport layer 161 comprising a compound of formula 1 and a second electron transport layer 162, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161. Alternatively, the electron transport layer stack (ETL) 160 comprises a first electron transport layer 161 and a second electron transport layer 162 comprising compound of formula 1, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161.

FIG. 3 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises an emission layer 150 and an electron transport layer stack (ETL) 160 comprising a first electron transport layer 161 that comprises a compound of formula 1, a second electron transport layer 162 that comprises a compound of formula 1 but different to the compound of the first electron transport layer, and a third electron transport layer 163, whereby the second electron transport layer 162 is disposed directly on the first electron transport layer 161 and the third electron transport layer 163 is disposed directly on the first electron transport layer 162.

FIG. 4 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, one first electron transport layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode electrode 190. The first electron transport layer (ETL) 161 comprises a compound of formula 1 and optionally an alkali halide or alkali organic complex. The electron transport layer (ETL) 161 is formed directly on the EML 150.

FIG. 5 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer stack (ETL) 160, an electron injection layer (EIL) 180, and a cathode electrode 190. The electron transport layer (ETL) 160 comprises a first electron transport layer 161 and a second electron transport layer 162, wherein the first electron transport layer is arranged near to the anode (120) and the second electron transport layer is arranged near to the cathode (190). The first and/or the second electron transport layer comprise a compound of formula 1 and optionally an alkali halide or alkali organic complex.

FIG. 6 is a schematic sectional view of an organic light-emitting diode 100, according to an exemplary embodiment of the present invention. The OLED 100 comprises a substrate 110, a first anode electrode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer stack (ETL) 160, an electron injection layer (EIL) 180, and a second cathode electrode 190. The electron transport layer stack (ETL) 160 comprises a first electron transport layer 161, a second electron transport layer 162 and a third electron transport layer 163. The first electron transport layer 161 is formed directly on the emission layer (EML) 150. The first, second and/or third electron transport layer comprise a compound of formula 1 that is different for each layer, and optionally an alkali halide or alkali organic complex.

Organic Semiconductor Layer

According to another aspect an organic semiconductor layer may comprises at least one compound of formula 1 and/or formula 1a.

According to one embodiment the organic semiconductor layer may comprises at least one compound of formula 1 and further comprises a metal, metal salt or organic alkali metal complex, preferably alkali metal complex, more preferably LiQ or alkali borate.

According to one embodiment, wherein at least one organic semiconductor layer is arranged between the emission layer and the cathode, preferably between the auxiliary electron transport layer and the cathode.

In another embodiment, the organic semiconductor layer is arranged between the emission layer and the electron transport layer.

According to one embodiment, the organic semiconductor layer is arranged between the first and second emission layer. The organic semiconductor layer can be an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, and more preferred an electron transport layer.

According to one embodiment, the organic semiconductor layer can be arranged between a photoactive layer and a cathode layer, preferably between an emission layer or light-absorbing layer and the cathode layer, preferably the organic semiconductor layer is an electron transport layer.

According to one embodiment, the organic semiconductor layer may comprise at least one alkali halide or alkali organic complex.

An organic semiconductor layer comprises a compound according to formula 1 or 1a is essentially non-emissive or non-emitting.

Organic Electronic Device

An organic electronic device according to the invention comprises at least one organic semiconductor layer, wherein at least one organic semiconductor layer comprises a compound according to formula 1 or 1a.

An organic electronic device according to one embodiment, which comprises at least one organic semiconductor layer that comprises a compound according to formula 1 or 1a, wherein this layer is essentially non-emissive or non-emitting.

According to one embodiment, the organic electronic device may comprises at least one organic semiconductor layer comprising a compound of formula 1 and/or 1a that is an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, more preferred an electron transport layer.

An organic electronic device according to one embodiment may include a substrate, an anode layer, an organic semiconductor layer comprising a compound of formula 1 and/or 1a, and a cathode layer.

The organic electronic device according to according to one embodiment may comprises at least one organic semiconductor layer, wherein the organic semiconductor layer comprising a compound of formula 1 and/or 1a is arranged between a photoactive layer and a cathode layer, preferably between an emission layer or light-absorbing layer and the cathode layer, preferably the organic semiconductor layer is an electron transport layer

The organic electronic device according to according to one embodiment may comprises at least one organic semiconductor layer comprising a compound of formula 1 and/or 1a, wherein the at least one organic semiconductor layer further comprises at least one alkali halide or alkali organic complex.

An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula 1 and/or 1a, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer comprising at least one compound of formula 1 and/or 1a is preferably arranged between the emission layer and the cathode layer.

An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one compound of formula 1 and/or 1a and further comprises at least one alkali halide or alkali organic complex.

An organic electronic device according to one embodiment comprises at least one organic semiconductor layer, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer comprising at least one compound of formula 1 and/or 1a is preferably arranged between the emission layer and the cathode layer. Preferably the at least one organic semiconductor layer is an electron transport layer.

An organic light-emitting diode (OLED) according to the invention may include an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) comprising at least one compound of formula 1 and/or 1a, and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.

An organic electronic device according to one embodiment can be a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell, and preferably a light emitting device. A light emitting device can be an OLED.

According to one embodiment the OLED may have the following layer structure, wherein the layers having the following order:

an anode layer, a hole injection layer, optional a first hole transport layer, optional a second hole transport layer, an emission layer, an electron transport layer comprising a compound of formula 1 according to the invention, an electron injection layer, and a cathode layer.

According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using:

-   -   at least one deposition source, preferably two deposition         sources and more preferred at least three deposition sources.

The methods for deposition that can be suitable comprise:

-   -   deposition via vacuum thermal evaporation;     -   deposition via solution processing, preferably the processing is         selected from spin-coating, printing, casting; and/or     -   slot-die coating.

According to various embodiments of the present invention, there is provided a method using:

-   -   a first deposition source to release the compound of formula 1         according to the invention, and     -   a second deposition source to release the alkali halide or         alkali organic complex, preferably a lithium halide or lithium         organic complex;         the method comprising the steps of forming the electron         transport layer stack; whereby for an organic light-emitting         diode (OLED):     -   the first electron transport layer is formed by releasing the         compound of formula 1 according to the invention from the first         deposition source and the alkali halide or alkali organic         complex, preferably a lithium halide or lithium organic complex         from the second deposition source.

According to various embodiments of the present invention, the method may further include forming on the anode electrode an emission layer and at least one layer selected from the group consisting of forming a hole injection layer, forming a hole transport layer, or forming a hole blocking layer, between the anode electrode and the first electron transport layer.

According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein

-   -   on a substrate a first anode electrode is formed,     -   on the first anode electrode an emission layer is formed,     -   on the emission layer an electron transport layer stack is         formed, preferably a first electron transport layer is formed on         the emission layer and optional a second electron transport         layer is formed,     -   and finally a cathode electrode is formed,     -   optional a hole injection layer, a hole transport layer, and a         hole blocking layer, formed in that order between the first         anode electrode and the emission layer,     -   optional an electron injection layer is formed between the         electron transport layer and the cathode electrode.

According to various embodiments of the present invention, the method may further include forming an electron injection layer on a first electron transport layer. However, according to various embodiments of the OLED of the present invention, the OLED may not comprise an electron injection layer.

According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:

an anode, first hole transport layer, second hole transport layer, emission layer, optional second electron transport layer, first electron transport layer comprising a compound of formula 1 according to the invention, optional an electron injection layer, and a cathode.

According to another aspect of the invention, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the electronic device is a display device.

Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects.

Preparation of Compounds of Formula 1

Compound of formula 1 may be prepared as described below.

Synthesis of D1:

2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine

A flask was flushed with nitrogen and charged with 2,4-dichloro-6-phenyl-1,3,5-triazine (100 g, 442 mmol), dibenzo[b,d]furan-3-ylboronic acid (75 g, 354 mol), Pd(PPh₃)₄(25.6 g, 22 mmol), and K₂CO₃ (153 g, 1106 mmol). A mixture of deaerated toluene/THF/water (1:1:1, 1110 mL) was added and the reaction mixture was heated to 65° C. under a nitrogen atmosphere for 2.5 h. The reaction mixture was cooled down to 5° C. and the precipitate was collected by suction filtration and washed with a minimal amount of toluene. After washing with water until the filtrate was pH neutral, the solid was washed with methanol and dried. Subsequently, the solid was dissolved in hot chloroform and filtered over a pad of silica. Additional chloroform was used to rinse the product completely. The filtrate was concentrated in vacuo to a minimal volume and n-hexane was added. After stirring overnight, the obtained precipitate was isolated by suction filtration, washed with n-hexane and dried. After purification by sublimation, 62.7 g (40%) of a white solid were obtained.

2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)-1,3,5-triazine

A flask was flushed with nitrogen and charged with 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (10 g, 27.95 mmol), 4,4,5,5-tetramethyl-2-(3-(9-phenyl-9H-fluoren-9-yl)phenyl)-1,3,2-dioxaborolane (13 g, 29.35 mmol), Pd(PPh₃)₄ (0.65 g, 0.56 mmol), and K₂CO₃ (7.7 g, 55.9 mmol). A mixture of deaerated THF/water (2:1, 150 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere for 18 h. After cooling down to room temperature, the THF was removed in vacuo, chloroform was added and organic phase was washed with water three times. The organic phase was dried over MgSO₄ and filtered over a silica pad. Additional chloroform was used to rinse the product completely. The filtrate was concentrated in vacuo to a minimal volume and n-hexane was added. After stirring overnight, the obtained precipitate was isolated by suction filtration, washed with n-hexane and dried to yield 16.6 g (93%) of a white solid. Final purification was achieved by sublimation. m/z=640 ([M+H]+).

Compound D2 was prepared in a similar manner. The Tg of compound D2 is 134° C.

Compounds of formula 1b and 1c may be prepared via a similar route, starting from the following compounds

General Procedure for Fabrication of OLEDs

For top emission devices, Examples 1 and comparative example 1, a glass substrate was cut to a size of 50 mm×50 mm×0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and cleaned again with UV ozone for 30 minutes. 100 nm Ag were deposited on the glass substrate at a pressure of 10⁻⁵ to 10⁻⁷ mbar to form the anode.

Then, 92 vol.-% Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) with 8 vol.-% 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) was vacuum deposited on the anode, to form a HIL having a thickness of 10 nm. Then, Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited on the HIL, to form a HTL having a thickness of 118 nm.

Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.

Then 97 vol.-% H09 (Sun Fine Chemicals) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals) as fluorescent blue dopant were deposited on the EBL, to form a blue-emitting EML with a thickness of 20 nm.

Then the hole blocking layer is formed with a thickness of 5 nm by depositing 2,4-diphenyl-6-(4′,5′,6′-triphenyl-[1,1′:2′,1″:3″,1′″:3′″, 1″″-quinquephenyl]-3″″-yl)-1,3,5-triazine on the emission layer.

Then, the electron transporting layer is formed on the hole blocking layer according to Examples 1 and comparative example 1 with a the thickness of 31 nm. The electron transport layer comprises 50 wt.-% matrix compound and 50 wt.-% of alkali organic complex. The composition is shown in Table 1.

Then, the electron injection layer is formed on the electron transporting layer by deposing Yb with a thickness of 2 nm.

Ag is evaporated at a rate of 0.01 to 1 Å/s at 10⁻⁷ mbar to form a cathode with a thickness of 11 nm.

A cap layer of Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine is formed on the cathode with a thickness of 75 nm.

The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.

To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured under ambient conditions (20° C.). Current voltage measurements are performed using a Keithley 2400 sourcemeter, and recorded in V. At 10 mA/cm² for top emission devices, a calibrated spectrometer CAS 140 from Instrument Systems is used for measurement of CIE coordinates and brightness in Candela. Lifetime LT of the device is measured at ambient conditions (20° C.) and 30 mA/cm², using a Keithley 2400 sourcemeter, and recorded in hours.

The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97% of its initial value.

The light output in external efficiency EQE and power efficiency (lm/W efficiency) are determined at 10 mA/cm² for top emission devices.

To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode.

To determine the power efficiency in lm/W, in a first step the luminance in candela per square meter (cd/m2) is measured with an array spectrometer CAS 140 CT from Instrument Systems which has been calibrated by Deutsche Akkreditierungsstelle (DAkkS). In a second step, the luminance is then multiplied by π and divided by the voltage and current density.

In bottom emission devices, the emission is predominately Lambertian and quantified in percent external quantum efficiency (EQE) and power efficiency in lm/W.

In top emission devices, the emission is forward directed, non-Lambertian and also highly dependent on the micro-cavity. Therefore, the external quantum efficiency (EQE) and power efficiency in lm/W will be higher compared to bottom emission devices.

Technical Effect of the Invention

As can be seen in Table 1, the Tg of compound of formula 1 is increased over the Tg of comparative example 1.

Top Emission Devices

In Table 1 is shown the performance of in organic electronic device comprising an organic semiconductor layer comprising a compound of formula 1 and an alkali organic complex.

In comparative example 1, compound ETM-1 was used as matrix compound:

In comparative example 1, the organic semiconductor layer comprises 50 vol.-% ETM-1 and 50 vol.-% LiQ. The operating voltage is 3.6 V, the cd/A efficiency is 7.5 cd/A and the lifetime is 72 hours.

In Example 1, the organic semiconductor layer comprises 50 vol.-% compound of formula 1 D1 and 50 vol.-% LiQ. The operating voltage is 3.7 V. The cd/A efficiency is improved to 8.1 cd/A and the lifetime is improved to 142 hours.

In summary, improved cd/A efficiency and/or improved lifetime may be achieved when the organic semiconductor layer comprises a compound of formula 1.

TABLE 1 Performance data of organic electroluminescent device comprising an organic semiconductor layer comprising a compound of formula 1 and an alkali organic complex Concen- tration of alkali cd/A organic Operating effici- Tg of Alkali complex Thick- voltage ency at matrix organic in the ness at 10 10 mA/ LT Matrix compound com- ETL ETL mA/cm² cm² 97 compound ( ° C.) plex (wt.-%) (nm) (V) (cd/A) (h) Comp.- ETM-1 113 LiQ 50 31 3.6 7.5 72 example 1 Example D1 126 LiQ 50 31 3.7 8.1 142 1

While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the present invention in any way. 

The invention claimed is:
 1. A compound of formula 1,

wherein X is selected from O or S; Ar¹ is selected from C₁ to C₁₆ alkyl or substituted or unsubstituted C₆ to C₂₄ aryl; Ar² is selected from C₁ to C₁₆ alkylene or is selected from unsubstituted arylene (C7) to (C11):

Ar³ is selected from C₁ to C₁₆ alkyl, substituted or unsubstituted C₆ to C₃₆ aryl or substituted or unsubstituted C₃ to C₃₆ heteroaryl; and wherein Ar¹ of substituted C₆ to C₂₄ aryl is mono or di-substituted, wherein the substituents of the substituted C₆ to C₂₄ aryl is selected from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl; and wherein Ar³ of substituted C₆ to C₃₆ aryl and Ar³ of substituted C₃ to C₃₆ heteroaryl is mono or di-substituted, wherein the substituents of the substituted C₆ to C₃₆ aryl and substituted C₃ to C₃₆ heteroaryl are selected from C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, partially or perfluorinated C₁ to C₁₆ alkyl, partially or perfluorinated C₁ to C₁₆ alkoxy, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, F or CN.
 2. The compound of formula 1 according to claim 1 having the formula 1a:


3. The compound of formula 1 according to claim 1 having the formula 1b:


4. The compound of formula 1 according to claim 1 having the formula 1c:


5. The compound of formula 1 according to claim 1, wherein Ar¹ is substituted or unsubstituted C₆ to C₁₂ aryl, wherein the substituents of the substituted C₆ to C₁₂ aryl is selected from C₁ to C₁₀ alkyl.
 6. The compound of formula 1 according to claim 1, wherein Ar³ is selected from substituted or unsubstituted C₆ to C₂₄ aryl, wherein the substituents of the substituted C₆ to C₂₄ aryl are selected from C₁ to C₁₀ alkyl or CN.
 7. The compound of formula 1 according to claim 1, wherein Ar¹ is selected from substituted or unsubstituted annelated C₆ to C₂₄ aryl, wherein the substituents of the substituted annelated C₆ to C₂₄ aryl is selected from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl.
 8. The compound of formula 1 according to claim 1, wherein Ar³ is selected from unsubstituted C₆ to C₂₄ aryl; and Ar¹ is selected from unsubstituted C₆ to C₂₄ aryl or C₁ to C₁₆ alkyl substituted C₆ to C₂₄ aryl.
 9. The compound of formula 1 according to claim 1, wherein Ar¹ is independently selected from B1 to B16 and A³ is independently selected from B1 to B53: wherein a) B1 to B6 are substituted or unsubstituted non-heteroaryl groups:

b) B7 to B16 are substituted or unsubstituted annelated non-heteroaryl groups:

c) B17 to B25 are dibenzofurane/dibenzothiophene group:

d) B26 to B28 are unsubstituted pyridine groups:

e) B29 to B46 are unsubstituted or substituted hetero arylene groups:

f) B47 to B48 unsubstituted annelated hetero arylene groups:

g) B49 and B50 are nitrile substituted phenyl groups

h) B51 to B53 are nitrile substituted biphenyl groups

wherein the substituent R² is independently selected from H, C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl.
 10. The compound of formula 1 according to claim 1, wherein Ar² is selected from unsubstituted arylene (C7).
 11. The compound of formula 1 according to claim 1, wherein the compound is selected from D1 to D11:


12. An organic semiconductor layer comprising at least one compound of formula 1 according to claim
 1. 13. The organic semiconductor layer according to claim 12, further comprises a metal, metal salt or organic alkali metal complex.
 14. An organic electronic device comprising an organic semiconductor layer according to claim 12, wherein at least one organic semiconductor layer comprises a compound selected from formula 1, 1a, 1b or 1c.
 15. The organic electronic device according to claim 14, wherein the electronic device is selected from a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell. 